CN1386763A - Surface modified nano cellulose crystal and its preparing process - Google Patents
Surface modified nano cellulose crystal and its preparing process Download PDFInfo
- Publication number
- CN1386763A CN1386763A CN 02115281 CN02115281A CN1386763A CN 1386763 A CN1386763 A CN 1386763A CN 02115281 CN02115281 CN 02115281 CN 02115281 A CN02115281 A CN 02115281A CN 1386763 A CN1386763 A CN 1386763A
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- crystal
- nano cellulose
- cellulose
- cellulose crystal
- modification
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- 239000013078 crystal Substances 0.000 title claims abstract description 67
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims description 10
- 230000008569 process Effects 0.000 title description 2
- 238000001035 drying Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 229920002678 cellulose Polymers 0.000 claims description 24
- 239000001913 cellulose Substances 0.000 claims description 24
- 238000012986 modification Methods 0.000 claims description 20
- 230000004048 modification Effects 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 8
- 230000010355 oscillation Effects 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 5
- 230000009514 concussion Effects 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 2
- 239000003814 drug Substances 0.000 abstract description 3
- 235000013305 food Nutrition 0.000 abstract description 3
- 230000015271 coagulation Effects 0.000 abstract 1
- 238000005345 coagulation Methods 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 20
- 238000003756 stirring Methods 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 230000009471 action Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 2
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000013462 industrial intermediate Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Abstract
A nano cellulose crystal with modified surface for easily dispersing it in water medium without coagulation is prepared from the nano cellulose crystal through carboxylmethylating its surface in water dispersion system and drying. It has wide applications in food, medicine, paper, etc.
Description
Technical field
The present invention relates to a kind of through surface modification, Yishui River dispersive nano cellulose crystal and method for making thereof.
Technical background
Mierocrystalline cellulose is the most extensive, the inexhaustible renewable resources in source that occurring in nature exists.Occur on earth after the crisis of Nonrenewable energy resources such as oil Mierocrystalline cellulose being degraded, deep processing is to obtain the focus that industrial chemicals and intermediate are various countries' research always.
At Chinese invention patent application (application number 00117261.1, application number 01107523.6) disclosed the method that has cellulose I crystal formation, crystal form of cellulose II and cellulose I and the nano cellulose crystal of II mixing crystal formation with natural cellulose preparation in, its profile can be bar-shaped, spherical or the ellipsoid shape, and the size of particle is between 5～100nm.These nano cellulose crystals have the physics-chem characteristic of the ordinary microcrystalline cellulose of differing from.
Ultra-fine and nano cellulose crystal has been widely used, and can be used as the additive and the weighting agent of food, field of medicaments, also can be used as the raw material in the novel material preparation.
The grain diameter of nano cellulose crystal is minimum, has huge specific surface and surface atom number, has special surface effects, as quantum tunneling effect, and unsettled coordinate bond etc.The surfactivity of nanoparticle is very big, response capacity also strengthens greatly, nano cellulose crystal still has cellulosic crystal formation simultaneously, can utilize the active group on its grape ring to carry out graft copolymerization, nano cellulose crystal can stable dispersion in aqueous phase system, can be the reaction medium graft reaction with water with suitable monomer, this be that other form Mierocrystalline cellulose can't be accomplished.
Because the nano cellulose crystal surface exists abundant hydroxyl, under drying regime, can form the intensive hydrogen bond between the nano cellulose crystal surface, the intensity of this hydrogen bond action is only second to the effect of chemical bond.In case exsiccant, be and formed this hydrogen bond between the powdered nano cellulose crystal, just form between the nano cellulose crystal and reunite, be difficult to physical method they redispersion.In order to stop the reunion that takes place because of hydrogen bond action between the nano cellulose crystal, make its equably redispersion in water, must carry out chemically modified to its surface.
In United States Patent (USP) 3539365, disclosed in microfine cellulose crystallite (the particle diameter minimum reaches micron order) by blend adding carboxymethyl cellulose, to overcome the reunion that the microfine cellulose crystallite takes place because of surperficial hydrogen bond action.Owing to can't guarantee that in the blend process carboxymethyl cellulose can be evenly distributed in the microfine cellulose, cause between some microfine cellulose crystallites because of the separation that does not have carboxymethyl cellulose produces hydrogen bond, thereby the reunion that can not break takes place in some microfine cellulose crystallites inevitably.This situation is particularly serious in nano cellulose crystal.
Technology contents
The objective of the invention is to overcome the deficiencies in the prior art, a kind of nano cellulose crystal through surface modification is provided, it can solve the reunion that takes place because of hydrogen bond action between the nano cellulose crystal effectively, make its equably redispersion in water.
Another object of the present invention provides the preparation method of this nano cellulose crystal through surface modification.
In order to overcome above-mentioned shortcoming, the invention provides a kind of nano cellulose crystal of surface modification, its profile is bar-shaped, spherical or the ellipsoid shape, the size of particle is between 5～100nm, the particulate skin is through carboxymethyl-modification, particulate inside still is Mierocrystalline cellulose, both can have cellulose I crystal formation, crystal form of cellulose II, also can have the crystal formation that mixes of cellulose I and II.
Provided by the invention through surface modification, Yishui River dispersive nano cellulose crystal realizes as follows: carboxymethyl-modification is carried out on the surface to nano cellulose crystal, carry out drying treatment then, obtain to be dispersed in powdery nano cellulose crystal in the water with this.
A kind of preparation method of surperficial carboxymethyl-modification nano cellulose crystal specifically is provided, its preparation process is in the aqueous dispersion of nano cellulose crystal, add sodium hydroxide, Mono Chloro Acetic Acid or sodium chloroacetate, in high-speed stirring, under sonic oscillation or the condition that leaves standstill, after when 0～100 ℃ of modification is handled one section, asking, drying handle the nano cellulose crystal of powdery surface modification, the add-on of wherein said sodium hydroxide is 0.5%～25% of a nano cellulose crystal weight, and the add-on of described Mono Chloro Acetic Acid or sodium chloroacetate is 1%～20% of a nano cellulose crystal weight.
Treatment time generally is subject to processing the influence of condition and required surperficial carboxymethylation degree, under ultrasonic concussion, the agitation condition than under the static condition, the required time shortens, especially ultrasonic concussion.There is certain influence the time of handling to surperficial carboxymethylation degree.Time lengthening does not generally have detrimentally affect.
Surface-modified nano Mierocrystalline cellulose crystalline preparation method provided by the invention can not carry out before nano cellulose crystal has drying in the later stage of nano cellulose crystal preparation process.
The surperficial carboxymethyl-modification of nano cellulose crystal provided by the invention, granule interior still keeps the structure of original nano cellulose crystal, crystal formation does not change yet, and still can have cellulose I crystal formation, crystal form of cellulose II, can have the crystal formation that mixes of cellulose I and II yet.The size of particle remains on asking of 5～100nm.But owing to surface carboxymethylation, overcome the agglomeration traits that takes place because of hydrogen bond action between the nano cellulose crystal, chemical modification method provided by the invention, modification is even, more superior than the simple segregation method that mixes carboxymethyl cellulose, the nano cellulose crystal behind the surperficial carboxymethyl-modification also easily equably redispersion in aqueous medium.This material has good application prospects at aspects such as food, medicine, papermaking, weaving and novel material preparations.
Embodiment
Embodiment 1
In the water dispersion of 1000g nano cellulose crystal, wherein contain the 10g nano cellulose crystal.Add 2.5g NaOH therein, stir and dissolve fully until NaOH.Add Mono Chloro Acetic Acid 1.8g again, constantly stir.Under 45 ℃, handle 12h, promptly obtain product after washing and the drying with sonic oscillation.
Embodiment 2
In the water dispersion of 1000g nano cellulose crystal, wherein contain the 10g nano cellulose crystal.Add Mono Chloro Acetic Acid 1g therein, add 2.5g NaOH after stirring evenly fully again, stir and dissolve fully until NaOH.Then, under 45 ℃, handle 16h, promptly obtain product after washing and the drying with sonic oscillation.
Embodiment 3
In the water dispersion of 1000g nano cellulose crystal, wherein contain the 10g nano cellulose crystal.Add sodium chloroacetate 1.2g therein, add 2.25g NaOH after stirring evenly fully again, stir and dissolve fully until NaOH.Then, handle 0.5h, under 25 ℃, leave standstill 52h again, promptly obtain product after washing and the drying with sonic oscillation.
Embodiment 4
In the water dispersion of 1000g nano cellulose crystal, wherein contain the 20g nano cellulose crystal.Add Mono Chloro Acetic Acid 2g therein, add 4g NaOH after stirring evenly fully again, stir and dissolve fully until NaOH.Then, handle 0.5h, under 32.5 ℃, leave standstill 48h again, promptly obtain product after washing and the drying with sonic oscillation.
Embodiment 5
In the water dispersion of 1000g nano cellulose crystal, wherein contain the 20g nano cellulose crystal.Add Mono Chloro Acetic Acid 0.2g therein, add 2.5g NaOH after stirring evenly fully again, stir and dissolve fully until NaOH.Then, handle 0.5h, under 32.5 ℃, leave standstill 48h again, promptly obtain product after washing and the drying with sonic oscillation.
Claims (4)
1, a kind of nano cellulose crystal through surface modification, its profile is bar-shaped, spherical or the ellipsoid shape, the size of particle is between 5～100nm, it is characterized in that the particulate skin is through carboxymethyl-modification, particulate inside still is Mierocrystalline cellulose, both can have cellulose I crystal formation, crystal form of cellulose II, also can have the crystal formation that mixes of cellulose I and II.
2, a kind of method for preparing nano cellulose crystal described in the claim 1 is characterized in that carboxymethyl-modification is carried out on the surface of nano cellulose crystal, carries out drying treatment then, obtains being dispersed in the powdery nano cellulose crystal in the water.
3, according to the method described in the claim 2, it is characterized in that in the aqueous dispersion of nano cellulose crystal, add sodium hydroxide, Mono Chloro Acetic Acid or sodium chloroacetate, under high-speed stirring, sonic oscillation or the condition that leaves standstill, after for some time is handled in 0～100 ℃ of modification, drying handle the nano cellulose crystal of powdery surface modification, the add-on of wherein said sodium hydroxide is 0.5%～25% of a nano cellulose crystal weight, and the add-on of described Mono Chloro Acetic Acid or sodium chloroacetate is 1%～20% of a nano cellulose crystal weight.
4,, it is characterized in that the method for the ultrasonic concussion of modification processing employing according to the method described in the claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021152810A CN1164617C (en) | 2002-05-27 | 2002-05-27 | Surface modified nano cellulose crystal and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021152810A CN1164617C (en) | 2002-05-27 | 2002-05-27 | Surface modified nano cellulose crystal and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1386763A true CN1386763A (en) | 2002-12-25 |
| CN1164617C CN1164617C (en) | 2004-09-01 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021152810A Expired - Fee Related CN1164617C (en) | 2002-05-27 | 2002-05-27 | Surface modified nano cellulose crystal and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1164617C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360604C (en) * | 2003-04-23 | 2008-01-09 | 中国科学院广州化学研究所 | Water dispersible nanometer avicel, its prep.and colloid therefrom |
| CN101772517B (en) * | 2007-08-10 | 2012-06-27 | 陶氏环球技术公司 | Nanoparticles of slightly oxidized cellulose |
| CN103214623A (en) * | 2013-05-11 | 2013-07-24 | 罗卫华 | Preparation method of surface-grafted modified nanocellulose crystal |
| CN103275336A (en) * | 2013-06-19 | 2013-09-04 | 天津科技大学 | Preparation method for cellulose crystal susceptible to re-dispersion after drying |
| CN104372687A (en) * | 2014-11-29 | 2015-02-25 | 滁州惠智科技服务有限公司 | Production method of cotton fiber/modified cotton fiber yarn-dyed cloth |
| CN104877033A (en) * | 2015-06-03 | 2015-09-02 | 西南大学 | Preparation method of carboxymethyl modified nano-crystalline celluloses |
| CN105148324A (en) * | 2015-08-31 | 2015-12-16 | 中原工学院 | Bone bionic materials built by mineralized nano cellulose whiskers and production method of bone bionic materials |
| CN105601756A (en) * | 2015-12-17 | 2016-05-25 | 华南理工大学 | Acetylation modification method for preparing nano cellulose |
| CN105603020A (en) * | 2016-01-21 | 2016-05-25 | 青岛农业大学 | Nanocrystalline cellulose preparation method |
| CN106279441A (en) * | 2016-09-11 | 2017-01-04 | 桂林理工大学 | A kind of preparation method of the Cellulose nanocrystal palpus of carboxylated modification |
| CN112707971A (en) * | 2019-10-24 | 2021-04-27 | 中国石油天然气股份有限公司 | Modified nano-cellulose crystal and preparation method thereof |
-
2002
- 2002-05-27 CN CNB021152810A patent/CN1164617C/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360604C (en) * | 2003-04-23 | 2008-01-09 | 中国科学院广州化学研究所 | Water dispersible nanometer avicel, its prep.and colloid therefrom |
| CN101772517B (en) * | 2007-08-10 | 2012-06-27 | 陶氏环球技术公司 | Nanoparticles of slightly oxidized cellulose |
| CN103214623A (en) * | 2013-05-11 | 2013-07-24 | 罗卫华 | Preparation method of surface-grafted modified nanocellulose crystal |
| CN103275336A (en) * | 2013-06-19 | 2013-09-04 | 天津科技大学 | Preparation method for cellulose crystal susceptible to re-dispersion after drying |
| CN103275336B (en) * | 2013-06-19 | 2015-06-10 | 天津科技大学 | Preparation method for cellulose crystal susceptible to re-dispersion after drying |
| CN104372687A (en) * | 2014-11-29 | 2015-02-25 | 滁州惠智科技服务有限公司 | Production method of cotton fiber/modified cotton fiber yarn-dyed cloth |
| CN104877033B (en) * | 2015-06-03 | 2018-07-06 | 西南大学 | A kind of preparation method of carboxymethyl modified nano-cellulose |
| CN104877033A (en) * | 2015-06-03 | 2015-09-02 | 西南大学 | Preparation method of carboxymethyl modified nano-crystalline celluloses |
| CN105148324A (en) * | 2015-08-31 | 2015-12-16 | 中原工学院 | Bone bionic materials built by mineralized nano cellulose whiskers and production method of bone bionic materials |
| CN105148324B (en) * | 2015-08-31 | 2018-02-16 | 中原工学院 | Bone biomimetic material that a kind of nano-cellulose whisker by mineralising is built and preparation method thereof |
| CN105601756A (en) * | 2015-12-17 | 2016-05-25 | 华南理工大学 | Acetylation modification method for preparing nano cellulose |
| CN105603020A (en) * | 2016-01-21 | 2016-05-25 | 青岛农业大学 | Nanocrystalline cellulose preparation method |
| CN105603020B (en) * | 2016-01-21 | 2019-05-10 | 青岛农业大学 | A kind of preparation method of nano cellulose crystal |
| CN106279441A (en) * | 2016-09-11 | 2017-01-04 | 桂林理工大学 | A kind of preparation method of the Cellulose nanocrystal palpus of carboxylated modification |
| CN112707971A (en) * | 2019-10-24 | 2021-04-27 | 中国石油天然气股份有限公司 | Modified nano-cellulose crystal and preparation method thereof |
| WO2021078086A1 (en) * | 2019-10-24 | 2021-04-29 | 中国石油天然气股份有限公司 | Modified nanocrystalline cellulose and preparation method thereof |
| CN112707971B (en) * | 2019-10-24 | 2022-03-29 | 中国石油天然气股份有限公司 | Modified nano-cellulose crystal and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1164617C (en) | 2004-09-01 |
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Granted publication date: 20040901 Termination date: 20120527 |